Water-insoluble disperse azo dyestuffs of cyclic aminobenzaldehyde acetals

ABSTRACT

AN AZO DYESTUFF OF THE FORMULA   1-((R-PHENYL)-N=N-),2-(HO-),3-((R2,R3-PHENYL)-NH-CO-)-NAPH   THALENE   WHEREIN R1 REPRESENTS A MEMBER SELECTED FROM THE ROUP   1,3-DIOXOL-2-YL 4-(H3C-)-1,3-DIOXOL-2-YL AND 4-(H3C-)-   1,3-DIOX-2-YL   AND R2 AND R3 EACH REPRESENT A MEMBER SELECTED FROM THE GROUP CONSISTING OF HYDROGEN, ALKYL OF 1 TO 4 CARBON ATOMS, ALKOXY OF 1 TO 4 CARBON ATOMS, CHLORINE AND NITRO; THE ZO DYESTUFF HAS IMPROVED LIGHT FASTNESS CHARACTERISTICS.

United States Patent 3,836,517 WATER-INSOLUBLE DISPERSE AZO DYESTUFFS OFCYCLIC AMINOBENZALDEHYDE ACETALS Richard C. Wilkinson, Warwick, R.I.,and Herman Hoffmann, Charles City, Iowa, assignors to American HoechstCorporation, Coventry, R.I. No Drawing. Filed July 1, 1971, Ser. No.159,064 Int. Cl. C09b 29/34, 29/36 US. Cl. 260152 2 Claims ABSTRACT OFTHE DISCLOSURE An azo dyestuif of the formula wherein R represents amember selected from the group AA. LJLL and O 0 CH CH3 The presentinvention concerns new azo dyestuffs which are especially suitable forcoloring polyester materials.

It is known that azo compounds produced from anilides 0f3-hydroxy-2-naphthoic acid and a variety of diazotizable anilines havefound application primarily for dyeing cotton fibers. With the advent ofpolyester fibers, these compounds have been examined as possibledisperse azo dyestuffs. As disclosed in US. Pat. 3,043,647, polyesterfibers can be dyed with compounds prepared by coupling the 2-methoxyandZ-ethoxy-anilides of 3- hydroxy-Z-naphthoic acid and diazotized anilinessubstituted with at least one of the following groups: hydrogen,halogen, alkoxy, nitro, cyano, phenylamino, alkoxyphenyl amino andbenzene azo. In many cases these azo compounds do not have sufficientsolubility in polyester fiber material to be useful as dispersedyestuffs unless certain penetrating agents (carriers) are used. Whilethese carriers increase the affinity of the dyestuffs to the polyesterfibers, they also cause the. undesirable effect of lowering the fastnessto light and must 'be removed from the fiber after the dyeing has beencompleted.

From US. Pat. 2,481,434 it is also known that acetals such asamino-phenyl-dioxolanes and amino-phenyldioxanes are useful in preparingdyes for general dye purposes, such as for textiles, plastics, pigments,etc., or any application where an aldehyde group increases the wherein Rrepresents a member selected from the group and R and R each represent amember selected from the group hydrogen, alkyl or alkoxy of 1 to 4carbon atoms, chlorine and nitro, and the naphthalene ring system may bereplaced by an anthracene ring system, has very valuable properties.

A dyestuff of the above formula shows very clean brilliant shades andhas excellent light fastness properties. In addition, the introductionof the acetal group enhances the affinity of the azo dyestuff topolyester materials due primarily to an increase in the solubility thatthe acetal group imparts to the azo dyestuff molecule for polyesters.

The azo dyestuff is prepared by known techniques of azo dyestuffchemistry, i.e., by diazotizing the cyclic aminobenzaldehyde-acetal andcoupling it with the anilide of 3-hydr0xy-2-naphthoic acid. Thisprocedure includes that the cyclic aminobenzaldehyde-acetal is for sometime exposed to the influence of astrong acid. As it is well 1 knownthat the acetals are very rapidly decomposed by Normally, the dyestuffcarrying an aldehyde group is present in amounts below 20% by weight,calculated on the total weight of the azo dyestutf, but in some cases upto 50% and more have been found. However, the content were prepared fromthe following coupling and amof dyestufi carrying an aldehyde group inthe range incomponents:

Example Coupling component Azo component sh d3-11ydroxy-2-napth-p-anisidide 2-(3-amino phenyl) 1,3 dioxolane Brill.orange.

3-hydroxy-Z-naphtho-o-phenetidide -do Do. 3-hydroxy-2-naphthanilide2-(3-aminophenyl)-4-methyl-l,3 dioxolane Do. 3-hydroxy-2-naphtho- -d0.Do. 6 S-hydroxy-Z-naphtho-o-pher .do.-. D 7.4'-chloro-3-hydroxy-2,5-dimethoxy-2-naphthanilide-- Red-orange 8-3-hydroxy-2-o-anthrotoluidide 9. 3-hydroxy-2-naphtho-o-to1uidide Brill.orange. 10 5'-ohloro-3-hydroxy-2',4-dimethoxy-Zmaphthanihde do- Orange.11 3-11ydroxy-2-methyI-Z-naphth-p-anisidide do 12-.4-chloro-3-hydroxy-2napl1tho-q-toluidid do Brill. orange 13..1-ehloro-3-hydroxy-2-naphtharnlide -do Orange, 14--3-hydroxy-Bmitro-2-naphthanil1de "d0-.. rill, orange 15..a-hydroxy-z-naphth-o-anisidide 2-(3-aminophenyl)-4-methyl-1,3 dioxaneo.16 3-hydroxy-Z-naphtho-o-phenetidide ..do D 1 dn 2-(2-amnophenyl)-t-methyl-l,3 dioxolane Yellow orange. 18 .--do-- 2-t4-mmophenyl)-4-methy1-1,3 dioxolane Red orange,

dieated is desirable as it improves the valuable properties We claim: ofthe dyestufi composition. 20 1. An azo dyestutr' of the formula Thecyclic aminobenzaldehyde-acetal used for the R1 preparation of thedyestufi disclosed is produced catalytically from the correspondingcyclic nitrobenzaldehydeacetal using a method similar to that describedin US. Pat. 2,481,434, where instead reduction is effected by nickel onkieselguhr at 400-600 p.s.i. hydrogen pressure t with water as adiluent, and the products are obtained :11 H high yield and purity. N

The cyclic nitrobenzaldehyde-acetal mentioned is prepared by methodssimilar to those described by E. J. R2 Salmi and K. Kyrki SuomenKemestilekti in 1913 97-102 O C (1946 CA. 41, 5480 d for nitroaeetais,when the mm benzaldehydes are heated with a slight molar excess of therequired glycol and catalytic amounts of hydrochloric 5 acid. Theremoval of water during the reaction shifts the equilibrium to give aquantitative yield of almost pure A A A cyclic nitrobenzaldehyde-acetal.0 0 Q 0 O 0 d EXAMPLE 1 -CH; an k orh 358 g. (2.0 mols) of2-(3-aminophenyl)-4-methyl-1,3- and R and R each represent a memberselected from dioxolane, 2 liters of Water and 3 kg. of ice were mixedthe group consisting of hydrogen, alkyl 0f 1 t 4 n and stirred, while400 ml. (4.0 mols) of concentrated hyaioms, alkOXY 0f 1 t0 4 carbonatoms. chlorine a drochloric acid (31.5%) were rapidly added during no umore than 10 minutes. The PH of the dissolved mixture 2. A compos1t1onof matter consisting of (a) an azo was kept at 1.0-2.0. To this solutionwas immediately dyestufl as clalmed Pp 1 and P to by Weight added duringno more than 10 minutes a solution of 151.8 of the .total .COmPPSmOH of(b) an i compound like g. (2.2 mols) of sodium nitrite dissolved in 500ml. of 50 that claimed m Claim 1 axcept that R1 15 3 wherein Rrepresents a member selected from the group water. The solution wastested with KI-starch paper to 0 determine the presence of a slightexcess of mtrous acid. -0

The solution was then adjusted to a pH of 7.0, and a solution of 614 g.(2.0 mols) of 3-hydroxy-2-naphtho-ophenetidide and 564 g. 1.0 mols) ofso sodium hy- References Cited droxide dissolved in 4 liters of waterwas slowly run in UNITED STATES PATENTS during a c upli g period of onehour. The pH was main- 2,468,277 4/1949 Strouse tained between 7.0-8.0during this coupling stage Th 3,609,134 9/ 971 Mory 260152 precipitateddyestufi was filtered, washed first with 2 3,043,647 7/1962 P et 260203liters of 5 percent sodium hydroxide and then finally with 24814349/1949 McQueen 260-152 water until nearly neutral. The filter cakecontained approximately 20-25% solid brilliant orange dyestufl? andFLOYD HIGEL Pnmary Exammer was dispersed without further dr in to ivethe final RAMSUER: Assistant Examine! Y g g paste.

US. Cl. According to the above-described procedure dyestuffs 260192, 204XR

